DE2433229A1 - METHOD FOR PRODUCING THIAZOLAZO COMPOUNDS - Google Patents

Description

HOECHST SHARESÖELLSCHAFT 2433229

File number: HOE 74 / F 191

Date: July 9, 1974 / Dr.ST/Hu

Process for the preparation of thiazole azo compounds

The present invention "relates to an improved method for the production of thiazolazo compounds.

Thiazolazo compounds from 2-aminothiazoles can be found in large quantities Extensive use as disperse and cationic dyes as well as pharmaceuticals.

These compounds are prepared by diazotizing 2-aminothiazoles with suitable coupling components coupled and the dyes obtained quaternized, if necessary, or by using 2-aminothiazoles as coupling components used.

Solid 2-aminothiazoles or their salts are used the end. However, 2- aminothiazole has toxic properties (see F.A. Patty, Industrial Hygiene and Toxicology, Vol. II, Toxicology, 1963, pages 2179-80) and Ullmanns Encyklopädie der technical chemistry (1966), volume 17, page 333) and is also relatively unstable and difficult to clean (See Ullmanns Encyklopadie der technischen Chemie (1953) »Volume 3» page 522), so that the production of such dyes is associated with a considerable technical effort.

It has now been found that these disadvantages can be avoided and the preparation of thiazolazo compounds using 2-aminothiazoles as diazo or coupling components can be done more easily and safely if you use the

- 2 -

5 0 9 885/1052

known V / eise obtained 2-aminothiazoles without Intermediate insulation used.

The procedure is carried out in the manner that one after one of the known methods (see TJllmanns Encyklopadie der technical chemistry (1953), volume 3, page 522, and Elderfield, Heterocyclic Compounds, Volume 5, page 484 ff (1957) "which produces 2-aminothiazole, for example by reacting thiourea with carbony halides according to the Scheme

R-. - CO - CH - Hal I I

H ₂ UTCSKH ₂

H. Shark

wherein R, hydrogen, an alkyl radical of 1 to 5 carbon atoms, an aralkyl, for example benzyl, aryl, for example phenyl or naphthyl, trifluoromethyl, cyano, Carboxylic acid, carboxylic acid ester, for example benzyl or allyl ester with 1 to 5 carbon atoms in the alkyl radical, carboxamide, carboxylic acid hydrazide, carbalkoxyalkyl, for example with an alkyl radical of 1 to 5C atoms, Carbamylalkyl, for example with an alkyl radical of 1 to 5 carbon atoms, or a heterocyclic radical and Rp Hydrogen, hydroxyalkyl, for example with an alkyl radical of 1 to 5 carbon atoms, an alkyl radical with 1 to 5 carbon atoms, an aryl, for example phenyl or naphthyl radical, carboxylic acid, carboxylic acid ester, for example benzyl cder-alkyl esters with 1 to 5 carbon atoms in the alkyl radical, Carboxylic acid amide, alkyl sulfone, for example

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with an Alley Ire st of 1 to 5C atoms, or aryl sulfone radical, "for example phenylsulfonyl radical," mean, where the Carboxylic acid or sulfonic acid amide groups, if appropriate substituents can contain, and the thus obtainable acidic aqueous solution of 2-aminothiazole directly for the further Implementation used.

The reaction of the thiourea with the carbonyl halide, expediently the chloride or bromide, according to equation (1) can be carried out in a suitable solvent.

Suitable solvents are, for example, water, mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acids, lower aliphatic carboxylic acids such as acetic acid, propionic acid or lactic acid, lower aliphatic ¹ alcohols such as methanol, ethanol, n- or iso-propanol or butanol, dimethylformamide, dimethylacetamide or dioxane or mixtures of the • solvents mentioned. Acetic acid or a mixture of acetic acid and propionic acid is particularly suitable, with water and / or a mineral acid also being able to be present.

The acidic solution of 2-aminothiazole obtained in this way can be used further directly. So you can then according to the usual Diazotize methods, for example by means of alkali metal nitrite and an inorganic acid, for example hydrochloric acid, Sulfuric acid or phosphoric acid, or by means of nitrosyl sulfuric acid.

The coupling with the coupling components can also be carried out in a manner known per se, e.g. in a neutral to acidic environment, optionally in the presence of sodium acetate or similar buffer substances which influence the coupling rate or catalysts, such as, for example, dimethylformamide, pyridine or its salts, can be carried out.

As coupling components come in o- or p-position to one Hydroxy group or a primary, secondary or tertiary amino group coupling aromatic or heterocyclic compounds into consideration, which are generally free of sulfonic acid group are.

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Among the series of suitable components which couple in the o- or p-position to a hydroxyl group are aromatic or heterocyclic hydroxy compounds and those compounds which have an enolizable or enolized Contain ketomethylene group located in a heterocyclic ring. Such connections are for example phenol substituted in the 2- or 4-position Derivatives of phenol, such as o- and p-cresol, p-chlorophenpl, 4-hydroxy-1,2-xylene, 4-hydroxyacetophenone and hydroquinone monomethyl ether, the derivatives of oc-naphtol substituted in the ^ -position, such as 4-chloro-1-naphtol, 4-methoxy-1-naphtol and 4-benzoyl-l-naphtol, β ^ naphtol and its derivatives, such as 6-bromo-2-naphtol, 7-hydroxy-2-methoxynaphthalene, 1-benzoylamino-7-n.aphtol and 4-benzolazo-1-amino-7-naphtol, as well 6-Hydroxyindaz ο1,6-Hydroxyquinoline, 8-Hydroxyquinoline, 4-hydroxy-1-alkyl-2-quinolones, 6-hydroxy-2-pyridones, 3-hydroxydiphenylamine, 2-hydroxycarbazole, 5 ~ hydroxybenzthiazole, 3-hydroxydiphenylene oxide and 5-py ^ azolones. Next to these monohydroxy compounds come as coupling components also polyhydroxy compounds coupling in the o-position to the hydroxyl groups the aromatic or heterocyclic series into consideration, for example resorcinol, benzoylresorcinol, Terephthaloyl bisresorcinol, 2,6-dihydroxynaphthalene, 2,4-dihydroxyquinoline and 3,6-dihydroxydiphenylene oxide.

Also suitable are alkyl or aryl amides of aromatic or heterocyclic hydroxycarboxylic acids or of acyl acetic acids, for example alkyl or aryl amides of 2,3-hydroxynaphthoic acids, 2-hydroxycarbazole-3-carboxylic acids, J-Hydroxydiphenylenoxyd ^ -carboxylic acids, acet-acetic acid , or benzoylacetic acid.

Of the coupling components that can be used in accordance with the process,

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which couple in the ο- or p-position to a primary, secondary or tertiary amino group are aromatic or hetero- ^; to name cyclic amino compounds. For example, as the primary amines which are suitable are aniline, toluidines xylidines, Anisidine, phenylenediamines, tolylene, Aminokresoläther _s alkoxyanilines, chloroanilines, 3-Acylaminoaniline, Dialkoxyaniline, naphthylamines and heterocyclic amines such as, for example, aminopyrimidine, 5-aminopyrazoles, 6- or 7-aminoindazoles or Amino quinolines. Compounds of the benzene or naphthalene series are suitable as secondary or tertiary amines, with the benzene or kaphthalene radical as further substituents, for example halogen atoms, alkyl, alkoxy, carbalkoxy, carboxy, alkylsulfonyl, carbamyl, sulfamyl, amino, May contain trifluoromethyl, acyl or acylamino groups. Substituents for the secondary or tertiary amino group are, for example, lower alkyl radicals having 1 to 5 carbon atoms

or aralkyl ^, cycloalkyl or aryl radicals of importance, in which optionally further substituents, such as halogen atoms, hydroxy, cyano, acyloxy, carbalkoxy, carbamyl, Dialkylamino, phenyl, alkoxy, acyl, pyridyl, dicarboximido, alkylsulfone, arylsulfone, alkylsulfonylamino, Sulfamyl or phenoxy groups can be represented .. In the tertiary amines, the alkyl groups can optionally also with one another or together with one Nitrogen or oxygen atoms form hydrogenated hetero rings, such as the piperidine, morpholine or piperazine ring.

Indoles, for example indole, 2-alkylindoles, 2-arylindoles, 1,2-dialkylindoles, and 1-alkyl-2-arylindoles are also used as coupling components or 1-alkylindoles and their derivatives substituted in the benzene nucleus, which are suitable in the alkyl or Aryl radicals may contain nonionic substituents. Suitable coupling components are also 1,2,3,4-tetrahydroquinolines or 1,2,3,4-tetrahydrobenzoquinolines, which contain optionally substituted alkyl radicals on the nitrogen.

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hold, as well as benzomorpholines, benzopiperazines, 2-methylene-1,3,3-trialkylindolines, 2-cyanomethylene-1,3-dialk, y! benzimidazolines, 1-alkyl-, 2-alkyl- or 1,2-dialkylpeiimidines, 4 , 5-dialkyl- or 4-, 5-diarylimidazoles, ary! Pyrazolines, for example l, 5-diphenyl-3,5-dimethylpyrazoline- .zl2, l- (a-ITaphthyl) -3,5 j5-trimethyl-pyrazoline- Δ 2, l-phenyl-3 «5,5-trimethylpyrazoline-Zl2 or 1- (2'-methoxy-5'-methylphenyl) -3,5i5-trimethylpyrazoline-Zi 2, 1,3-indanedione, 2,6- Dihydroxy-3-cyano-4-alkylpyridines, 2,6-diamino-3-cyano-4-alkylpyridines. 2,6-Bisalkylamino-4-phenylamino-pyriniidine, or 2,4-Bisalkylamino-6-phenylamino-pyrimidine, wherein the Alkylrestcbevorzugt 1 to 5 C - contain atoms.

The coupling components can optionally also be water-solubilizing agents Groups, such as sulfonic acid or sulfato groups, contain.

If the 2-aminothiazoles are substituted in the 5-position, they can also be used as coupling components and by coupling with diazotized aromatic or heterocyclic ones Amines are converted into the azo compounds.

The alkylation of the azo compounds, which may be used is at elevated temperature, if necessary with the addition of acid-binding agents such as magnesium oxide, magnesium carbonate, Soda, calcium carbonate or sodium bicarbonate and optionally under pressure. The most favorable conditions in each case can easily be determined through a preliminary test.

If appropriate, the alkylation can also be carried out in water.

Alkyl halides, aralkyl halides, Haloacetamides, ß-halopropionitriles, halohydrins, alkylene oxides, acrylic acid amide, alkyl esters of sulfuric acid or alkyl esters of organic sulfonic acids.

Suitable alkylating agents are, for example, Methy1-

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'chloride, bromide or iodide, ethyl bromide or iodide, propyl bromide or iodide, benzyl chloride, chloroacetamide, ß-chloropropionitrile, Ethylene chlorohydrin, dimethyl sulfate, benzenesulfonic acid methyl ester, p-toluenesulfonic acid methyl, ethyl, propyl or butyl ester. The alkylation is expediently carried out in one inert organic solvent, for example in a hydrocarbon, chlorinated hydrocarbon or nitrohydrocarbon, such as benzene, toluene, xylene, tetrachloroethane, chloroform, carbon tetrachloride, mono- or dichlorobenzene or nitrobenzene, in an acid amide or acid anhydride, such as dimethylformamide, N-methylacetamide or acetic anhydride, in Dimethyl sulfoxide or in a ketone such as acetone or methyl ethyl ketone. Instead of an organic solvent, it is also possible to use an excess of the alkylating agent.

Thiazolazo- or thiazolium azo compounds of the following formula / Aj to (C)

S N = Ji-K

E,

D-N = N

S '^ N = E-K

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in which E, and R _{2 have} the meaning given above, K is the radical of a coupling component, D is the radical of a diazo component, Alk is a lower alkyl radical. and X is an anion customary in cationic dyes.

The thiazolazo compounds of the formula ( A, J and (C)) obtainable according to the invention are suitable, provided they are free of sulfonic acid groups, excellent for dyeing and printing synthetic fibers, for example made from polyacrylonitrile or from copolymers of acrylonitrile with other vinyl compounds such as acrylic esters , Acrylic amides, vinyl pyridine, vinyl chloride or vinylidene chloride, or from copolymers of dicyanethylene and vinyl acetate, as well as from acrylonitrile block copolymers, fibers made of polyurethanes, polypropylene, cellulose tri- and 2 1/2 acetate and in particular fibers made of polyamides, such as polyamide 6, polyamide 6, 6 or polyamide 12 and from aromatic polyesters, such as those made from terephthalic acid and "ethylene glycol or lj ^ - dimethylolcyclohexane, and copolymers made from terephthalic and isophthalic acid and ethylene glycol. If the compounds of the formula ( A J and ( C J water-solubilizing groups, such as Sulphonic acid groups contain, they are suitable for Dyeing of wool and polyamide fibers. '

The compounds of the formulas (B) and! D J are suitable for dyeing or printing tannic cellulose fibers, silk, leather or fully synthetic fibers, such as acetate silk, polyamide fibers or acid-modified polyamide or polyester

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fibers, but especially of polyacrylonitrile or polyvinylidene anide containing fibers. The dyeings available on these fibers are usually very strong and possess generally good light and wet fastness properties, for example good washing, fulling, dyeing, carbonizing, chlorine and Perspiration fastness, as well as good decatur, steam, ironing, rubbing and solvent fastness.

The Thiazο! Azo compounds of the formula ΓA J in which K is the radical of a di-aminopyridine, may also, for example in the form of their water-soluble salts, are also used as bactericides.

The following examples serve to illustrate the invention Procedure. The parts by weight are related to the parts by volume as the kilogram is to the liter.

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example 1

a.) 22.8 parts by weight of thiourea are introduced into 120 parts by volume of glacial acetic acid. To this suspension is added dropwise at 40-5O ⁰ C 52.3 parts by weight of 45% aqueous chloroacetaldehyde solution, stirred for 2 hours at 40-50 C and stirred and cooled to 0 ⁰ C. 72 parts by weight of nitrosylsulfuric acid (42.3%) are run into this 2-amino-thiazole-containing solution at 0-5 ° C. with thorough stirring, the mixture is stirred for 30-60 minutes while the excess nitrite remains and the excess of nitrite is then destroyed with amidosulfonic acid. In the yellow colored clear diazo solution is allowed at 0-20 ⁰ C, a solution of 53 weight st rush 3-methyl-phenyl-morpholine in 60 parts by volume of glacial acetic acid shrink, stirred for 1 hour at 25 ° C. and poured the reaction mixture to I5OO parts by weight of ice water . The pH is adjusted to 3 with sodium hydroxide solution. The resulting crystalline dye is filtered off with suction and washed thoroughly with water. After drying 66 parts by weight of dye of the formula

Water well after washed. Obtained after de: m drying at 60.degree

HC - - \
/ - N = N -ί
V / CH ₂ - CH ₀ Ii S. /
CH,
ο 2 ^ HC - CH ₂ ^ >

which is suitable for dyeing polyesters.

b.) 29 parts by weight of this dye are dehydrated azeotropically with 300 parts by volume of toluene, then clarified with activated charcoal and kieselguhr. 1 part by weight of magnesium oxide is added to the filtrate. With stirring is added dropwise at 80-90 ⁰ C, a solution consisting of 10 parts by volume of dimethyl sulfate and 25 parts by volume of toluene. The mixture is subsequently stirred at 80-90 ° C. for about 7 hours until the quaternization is complete. The crystalline dye is filtered off with suction and washed thoroughly with toluene.

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After drying, 39 parts of dye of the formula are obtained

TM J

HG - s'

the acid modified polyacrylonitrile in shining Dyes violet shades with excellent colouristic fastness properties.

c.) Instead of the chloroacetaldehyde used in the preparation of the 2-amino-thiazole, equivalent amounts of bromacetaldehyde, chloroacetaldehyde-dimethyl- or diethylacetal, bromoacetaldehyde-dimethyl- or diethyl acetal, 'acetic acid- <^ _t ß -dichloro- or -dibromoethyl ester, bis- ( <L , ß-dichloro- or -dibromo-ethyl) ether, ck , ß-dichloroethyl or - «^, ß-dibromoethyl or -butyl or isoamyl ether or propionic acid- dichloro or dibromoethyl ester are used.

Example 2 ^!

a.) 9.1 parts by weight of thiourea are introduced into 60 parts by volume of glacial acetic acid. To this suspension is added dropwise at 40-50 ⁰ C 32.8 pbw of 4-5% aqueous Bromacetaldehydlösung. The mixture is left for 2 hours at about 50 ⁰ C, then stirred for 12 hours at room temperature and cooled subse- * ßend from to ⁰ C. At 0-5 ° C with 30 parts by weight of nitrosyl sulfuric acid (4-2.3% ig ) diazotized and the reaction mixture stirred for 30 minutes with excess nitrite. The excess nitrite is destroyed with sulfamic acid. The resulting diazo solution is added dropwise to a receiver containing 200 parts by volume of ice water and 16 parts by weight of N-methyl-N-cyanoethylaminobenzene and the mixture is left at 20-25 ° C. for 1 hour

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stir, v / whether the sulfate of the dye is partially precipitated. Dilute with 1000 parts by volume of water and put through. Add dropwise sodium hydroxide solution to a pH of 4. The dyestuff base, which is obtained in crystalline form, is filtered off with suction and washed free of salt with water. After drying at 60 ^° C., 22 parts by weight of dye of the formula are obtained

^HC " ^SX CH CH - CN

b.) I3.5 parts by weight of this dye are dehydrated azeotropically with 300 parts by weight of chlorobenzene. After addition of 1 part by weight of MgO is added dropwise at about 40 ⁰ C a solution of 5 parts by volume of dimethyl sulfate in 25 parts by volume of chlorobenzene · a, stirred for 1 hour at 4O ⁰ C and 7 hours at 80-90 ⁰ C until complete quaternization of the dye after and sucks off the crystalline dye. It is washed well with chlorobenzene. After drying - at 60 ^° C., 16 parts by weight of dye of the formula are obtained

HC-N

W / ^{x = /} \ GH, SO ^

HC-S ^υι1 2 "2"

which dyes acid-modified polyacrylonitrile fibers in bright violet tones with good fastness properties.

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Example 3 .

c.) I5.2 parts by weight of thiourea are suspended in 80 volumes of ile glacial acetic acid. At about 50 ⁰ C are added dropwise 35 parts Gewichtε-Ghloracetaldehyd (45%) and stirred for 2 hours at 50 ⁰ G after. At 0-5 ° G, 46 parts by weight of nitrosyl-sulfuric acid (42.3%) are diazotized, the reaction mixture is stirred at about 5 ° C. for 30 minutes and the excess nitrite is destroyed with sulfamic acid. To this diazo solution, a solution of 38 parts by weight of N-cyanoethyl-N-phenäthylanilin in 180 weight parts of sulfuric acid are added dropwise at 0-10 ⁰ C (40%). After the end of the inlet temperature to "20 to 25 ⁰ G is allowed to rise and stirred for 30 minutes at 20-25 ° C after. Under external cooling and maintaining the temperature of about 25 ° C is added dropwise 160 parts by volume V / ater one. The sulfate the dye separates out and is filtered off with suction after stirring for 2 hours.

b.) For quaternization, the moist filter cake is suspended in 95 parts by volume of water and adjusted to pH 9.5 with 3 parts by weight of magnesium oxide. After addition of a further 7 parts by weight of magnesium oxide is quaternized in 1 hour at about 30 ⁰ G under weak external cooling with 45 parts by volume of dimethyl sulfate. and then stirred at 30 ° C. for 3 hours. To destroy any residual amounts of dimethyl sulphate, 4 parts by volume of ammonia solution (approx. 25%) are added and the mixture is stirred for another 30 minutes at 30 ° C. It is then diluted with 500 parts by volume of water and adjusted to pH 1.7 with sulfuric acid. The sulphate of the dye - separates out in crystalline form. After 3 hours of stirring, it is sharply suctioned off. After drying at 60 ^° C., 56 parts by weight of dye of the formula are obtained

HC - S '^ GH ₂ -CH ₂ - /

SO,

- 14 -

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The dye dyes acid-modified polyacrylonitrile fibers in purple tones with very good colouristic properties.

Example 4

a.) 15.2 parts by weight of thiourea are suspended in 60 parts by volume of glacial acetic acid and 20 parts by volume of water. 18.5 parts by weight of chloroacetone are added dropwise at 25 ° C. The temperature rises to approx. 60-65 ° C. The reaction mixture is refluxed for 2 hours, cooled to ⁰ ° C., and 10 parts by volume of sulfuric acid (95%) are added. Then 60 parts by weight of nitrosylsulfuric acid (42-3%) are added dropwise at 0-5 ° C x ^. The Diazole solution is stirred for 30 minutes and then added at 10-20 ⁰ G to a fine suspension of 41 parts by weight of dibenzylaniline in 300 parts by volume of glacial acetic acid and 400 parts by volume of water, stirred for 1 hour at 20-25 ° C, diluted with 2000 parts by volume of ice water and mixed with Sodium hydroxide solution adjusted to pH 3-4. The resulting dye is filtered off with suction and washed with water. After drying, 44 parts by weight of dye of the formula are obtained

CH-S

b.) 40 parts by weight of this dye can, as in Example 1 described, are quaternized to the dye of the formula below

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The dye obtained dyes acid-modified polyacrylics nitrile fibers in reddish shades of blue with very good coloristic properties.

Example 5

If, instead of the chloroacetone, the equivalent amount of W -CMor- or bromoacetophenone is used in Example 4, the dye of the formula is obtained

Example 6

9.1 points by weight of thiourea are suspended in 36.5 parts by volume of glacial acetic acid. At 40-50 ⁰ C is added dropwise 19.8 GewichtsteileiO-chloroacetoacetic acid ethyl ester a, stirred for 2 hours at 40-50 ⁰ C, cooled to 20 ⁰ C. are then at -20-25 ° C successively 5 parts by volume sulfuric acid (95%) un <3. Add 10 parts by volume of water. This equipment is ^{cooled to 0} ° C. and diazotized at 0-5 ° C. by dropwise addition of 26 parts by weight of nitrosylsulfuric acid (4-2.3%). The mixture is stirred for 30 minutes, the excess nitrite is destroyed with sulfamic acid and a solution of 16 parts by weight of 3-chlorophenylmorpholine in 50 parts by volume of glacial acetic acid is added dropwise to the diazo solution at 5-15 ° C. The mixture is stirred for 1 hour at 20-25 ° C., poured onto 1000 parts by volume of ice water and adjusted to pH 4-5 with sodium hydroxide solution. The dye is extracted with 500 parts by volume of chlorobenzene. The chlorobenzene dye solution is dehydrated azeotropically and, as described in Example 2, with 10 parts by volume of dimethyl

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sulfate quaternized. 25 parts by weight of the dye are obtained substance of the formula

HC-S

the acid modified polyacrylonitrile fibers in reddish tones Dyes shades of blue with very good coloristic fastness properties.

Example 7

18.2 parts by weight of thiourea are suspended in 75 parts by volume of glacial acetic acid. At 40-50 C are added dropwise 42 parts by weight Chloracetaldehydlosung (45%) a, stirred for 2 hours at 40-50 ⁰ C, then 12 hours at room temperature. At 0-5 C, nitrosylsulfuric acid is added with 60 parts by weight

ο 42.3% diazotized, stirred for 30 minutes at O-5C and the Excess nitrite destroyed with amidosulfonic acid. That prepared Diazo solution is immersed in a solution of 14.4% by weight steep 2-oxynaphthalene in 50 parts by volume of dimethylformamide come in. It is then diluted with 1000 parts by volume of ice water and adjusted to pH 4 with sodium hydroxide solution. The mixture is stirred for 1 hour, the dye is filtered off with suction and washed with water. After drying, 23 is obtained Parts by weight of dye of the formula

HC-S

σ -

HC-N

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which is used for dyeing polyester fibers and for manufacturing of metal complex dyes.

Example 8

The preparation and diazotization of the 2-aminothiazole is carried out analogously to Example 7. The diazo solution is left at 20-25 ° C. in a solution of 60.5 parts by weight of 2-hydroxynaphthalene-3-carboxylic acid (2'-ethoxy) anilide in 500 volumes. share dimethylformamide, stir 30 minutes after y dilute with 3000 parts by volume of water and adjust to a pH of 4-5 with sodium hydroxide solution. The crystalline dyestuff is filtered off with suction and washed thoroughly with water. After drying, 80 parts by weight of a dye of the formula are obtained

HC -

OH CO NH

Example 9

The preparation and diazotization of 2-amino thiazole takes place analogously to Example 3.

In the diazo solution is added dropwise at 0-10 ⁰ C, a solution of 20.7 parts by weight of l-methyl-2-phenyl-indole in 60 parts by volume of dimethylformamide, stirred for 30 minutes at 10-15 C and after pouring the coupling mixture in 1000 parts by volume of ice water , which is adjusted to a pH value of 4-5 with sodium hydroxide solution. The resulting crystalline dye is filtered off with suction and washed with water.

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After drying, 30 parts by weight of dye are obtained the 'formula

HO-N HG -

which, as described in Example 2, are quaternized can, with about 31 parts by weight of the dye Formula·

HC - N ^ ^

^e / C - N = N -rp- ^ l CH SO

receives the acid modified polyacrylonitrile fibers in colors bright red tones with very good coloristic properties.

Example 10

The production and diazotization of 2-amino-thiazoles takes place analogously to Example 7.

The diazo solution is left in a solution of 56 parts by weight N-ethyl-F-phenylaminoethaiisulfonic acid in 4-00 parts by volume Running in water. The deep brown-red colored coupling solution is made alkaline with sodium hydroxide solution and then stirred for a few minutes. The dye of the formula

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^X _C - N = N - ^

^HC ~ ^S CH ₀ -GH ₀ -SO _x Na

2 d t>

is suctioned off and washed with saline solution. He dyes wool from an acid dye bath in red-brown shades.

Example 11

18.2 parts by weight of thiourea are suspended in 75 parts by volume of glacial acetic acid. At 40-50 ⁰ C (45% strength) are added dropwise 4-2 weight 'share a chloroacetaldehyde solution, stirred for 2 hours at ⁰ C to 4-0-50 and cooled to room temperature ab.Zu this solution is added dropwise at 10-20 ⁰ C a diazo solution of 27.6 parts by weight of 4-nitroaniline prepared in a known manner. A pH of 4 is set with aqueous soda solution or sodium hydroxide solution, the coupling commencing. Stirring is continued for 30 minutes and the dye is sucked off and dries it off, giving 64 parts by weight of the dye of the formula

HC-N

C - NH, O ₂ N - < ^x > - N = NC-

Example 12

The preparation and diazotization of 2-amino-thiazol occurs analogously to Example 3. It is allowed to the diazo solution at 0-10 ⁰ C in an initial charge of 7.3 parts by weight of 5-amino -1-methyl-pyrazol ^ _n 2OC parts by volume of ice-water shrink,

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stirred for 1 hour at 10-15 C and then neutralized with caustic soda. The resulting crystalline dye is filtered off with suction and washed well with water. After drying you get. 15 parts by weight of the dye of the formula

HC
II > - S. - N = N - C. - CH Il
HC H ₂ N ' K N
I. - I.
CH,
3

which, as described in example '2, quarternates one Dye of the formula

HC-IC ^ · _θ

- N = N - C - CH CH _x SO

H Il

^ C N

H ₂ N -N _n /

supplies. This quaternary dye stains acid-modified ones Polyacrylonitrile fiber in bright golden yellow tones with very good coloristic properties.

Example 13

a.) -9 | 1 part by weight of thiourea is suspended in 36.5 parts by volume of glacial acetic acid. The mixture is left at 40-50 ⁰ C during 1 hour 19.8 parts by weight <* .- chloroacetoacetic acid ethyl ester dropwise, stirred for 2 hours at 50-6O ⁰ C. and cooled to 20 ⁰ C. Then it is added dropwise at 20-25 ° C

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with external cooling successively 10 parts by volume of sulfuric acid (95%) and. 10 parts by volume V / ater. This mixture is ^{cooled to 0} ° C. and diazotized at 0 ° -5 ° C. with 26 parts by weight of nitrosylsulfuric acid (42.3%). The mixture is allowed to stir for 30 minutes with a remaining excess of nitrosylsulfuric acid, which is then destroyed with sulfamic acid. The diazo solution thus obtained is slowly added at 0-10 ° C. to a receiver containing 15.2 parts by weight of N-ethyl-N-ß-cyanoethylaniline in 200 parts by volume of ice water. The reaction mixture is stirred for 30 minutes, diluted with 1,000 parts by volume Eisv / ater and with sodium hydroxide to a pH of 4-5 gestellt.Der precipitated dye is filtered off and g at 60 ⁰ C (
formula

60 ⁰ C dried. 27 parts of the dye are obtained

H ₇₁ C -CN

U \
CN =

H ₅ C ₂ OOC -CS ₂₂

b.) 27 parts by weight of this dye are heated to boiling in 500 parts by volume of chlorobenzene and clarified with activated charcoal and kieselguhr. 1 part by weight of magnesium oxide is added to the filtrate. With stirring is added dropwise at about 4-0 C a solution of 10 parts by volume of dimethyl sulfate in 25 parts by volume of chlorobenzene and stirred for 1 hour at 4-0 ⁰ C and then for 5 hours at 80-90 ⁰ C. after. The resulting dye is filtered off, washed with chlorobenzene, and dried at 60 ⁰ C. 28 parts by weight of the dye of the formula are obtained

Θ C - N = N
/

H ₅ C ₂ OOC-C-S, CH ₂ -CH ₂ -ClT

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which dyes acid-modified polyacrylonitrile fibers in bright violet tones and has excellent properties.

Example 14

Be used in place of Example 13 · * - -Chloracetessigsäure-ethyl ester used equivalent amounts <L -Chloracetessigsäuremethylester so after diazotization ^ Eupplung and subsequent quaternization obtained the analog dye of formula

CH ₅

HC - C - IT ^
³ _e \ - N - N

π rnnr r q '^ CHp-CHp-CN

the acid-modified polyacrylonitrile fibers in colors purple tones with very good coloristic properties.

example

Instead of the ethyl chloroacetoacetate used in Example 13 equivalent amounts of "^ -chlorobenzoyl acetic acid ethyl ester are used, so.be obtained after diazotization, coupling with 3-N, IT-diethylamino-tolu.ol and subsequent quaternization with dimethyl sulfate in chlorobenzene Solution the dye of the formula

φ C - Έ = Ή - C - S

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the acid modified polyacrylonitrile fibers in reddish tones Shades of blue with very good colouristic properties stains.

Example 16

Substituting in place of the <L used in Example 13 -Chloracetessigsäure-ethyl ester equivalent amounts of 3-chloro-propane-dione 2.4-one, is obtained by diazotization, coupling with 3-N, N-diethylamino-toluene, and subsequent quaternization with dimethyl sulfate solution in.chlorbenzolischer the dye of the formula

H, C - C - Ή "3

C - N = N ^{- f N} > - IT

H _x CC - C - S '

⁵ Il O

the pig? modified polyacrylonitrile fibers in blue Dyes shades with very good coloristic properties.

509885/1052

Claims (4)

? Λ "HOE 2 # ί> 3.2ΐ2 9 claims: 1.) Process for the preparation of you thiazolazo compounds under "- ' Use of 2 ~ aminolhiazoethes as diazo or coupling components, characterized in that the 2-aminothiazoles obtained in a known manner are used without intermediate isolation. 2.) The method according to claim 1, characterized in that the 2-aminothiazoles are diazotized and with Kupp ment sko components clutch. 3.) Process according to claim 1, characterized in that the 2-aminothiazoles with diazotized aromatic odea? heterocyclic amines. 4.) Thiazο! Azo compounds, which by a process of Claims 1, 2 or 3 were made. 509885/10 52
ORIGINAL INSPECTED